In this work, persulfate (S2O82-, PS) was introduced to the photoelectrocatalytic (PEC) system, which consisted of a gamma-Bi2MoO6 photoanode and a copper foil cathode (Bi2MoO6/Cu/PEC/PS system). Significant enhancement of diclofenac sodium (DCF) degradation efficiency was observed in this system under visible light irradiation. At an applied bias of 1.5 V and initial solution pH of 5.62, the removal efficiency of DCF with an initial concentration of 10 mg/L was increased from 19.4% in the PEC process to 86.3% in the PEC process with 10 mM PS addition. The pseudo-first-order kinetic rate constant of DCF degradation was increased from 0.1112 h(-1) to 1.0498 h(-1). Active free radicals involving SO center dot(-)(4) and HO center dot were produced in this process, which were confirmed by electron spin resonance analysis. Furthermore, the surface variation of copper foil cathode was characterized by FE-SEM, GI-XRD, XPS and in situ Raman spectroscopy. It was demonstrated that Cu2O formed on the surface in the reaction process with the S2O82- addition, which was further confirmed by the photoelectrochemical analysis of the cathode. The surface Cu(0)-Cu(l)-Cu(II)-Cu(0) redox cycle of cathode was proposed, which was responsible for the persulfate activation, leading to the generation of free radicals. This work may provide a new perspective on the combined utilization of different technologies for catalytic contaminant removal. (C) 2017 Published by Elsevier B.V.